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Article Dans Une Revue Journal of Computational Chemistry Année : 2019

Electronic structure and optical properties of isolated and TiO 2 ‐grafted free base porphyrins for water oxidation

Résumé

Seven free base porphyrins employed in dye-sensitized photoelectrosynthetic cells are investigated with the aim of benchmarking the ability of different Density Functional Theory and Time Dependent Density Functional Theory approaches in reproducing their structure, vertical and E0-0 excitation energies and the energy levels alignment (red-ox properties) at the interface with the TiO2. We find that both vertical and E0-0 excitation energies are accurately reproduced by range-separated functionals, among which the wB97X-D delivers the lowest absolute deviations from experiments. When the dye/TiO2 interface is modeled, the physical interfacial energetics is only obtained when the B3LYP functional is employed; on the other hand, M06-2X (54% of exchange) and the two long-range corrected approaches tested (CAM-B3LYP and wB97X-D) excessively destabilize the semiconductor conduction band levels with respect to the dye’s lowest unoccupied molecular orbitals (LUMOs), predicting no pathway for electron injection.
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Dates et versions

hal-02395781 , version 1 (12-11-2021)

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Syrine Daoudi, Abderrahmane Semmeq, Michael Badawi, Xavier Assfeld, Youssef Arfaoui, et al.. Electronic structure and optical properties of isolated and TiO 2 ‐grafted free base porphyrins for water oxidation: A challenging test case for DFT and TD‐DFT. Journal of Computational Chemistry, 2019, 40 (29), pp.2530-2538. ⟨10.1002/jcc.26027⟩. ⟨hal-02395781⟩
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